CN110252417B - Titanate nanocone/polyacrylonitrile nanofiber composite material and preparation method thereof - Google Patents
Titanate nanocone/polyacrylonitrile nanofiber composite material and preparation method thereof Download PDFInfo
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 81
- 239000002121 nanofiber Substances 0.000 title claims abstract description 58
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000002110 nanocone Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000010041 electrostatic spinning Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000009987 spinning Methods 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 30
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 10
- 229940043267 rhodamine b Drugs 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- KUKFKAPJCRZILJ-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC#N.OC(=O)C=C KUKFKAPJCRZILJ-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/23—
-
- B01J35/39—
-
- B01J35/59—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a titanate nanocone/polyacrylonitrile nanofiber composite material and a preparation method thereof. Using polyacrylonitrile nano-fiber as carrier, firstly depositing amorphous TiO on its surface 2 As a seed layer, titanate nanocones are then deposited in a solution containing precursors and morphology control agents. The deposition of the titanate nanocone increases the specific surface area of the fiber composite material, the adsorption capacity of the fiber composite material on pollutants is enhanced, and the one-dimensional structure of the titanate nanocone can improve the transmission capacity of a photo-generated carrier, promote the separation of photo-generated electrons and cavities, and is beneficial to the enhancement of the photocatalytic degradation capacity. The fiber composite material provided by the invention has the advantages of simple preparation process, mild reaction conditions, low energy consumption, environmental friendliness and wide application.
Description
Technical Field
The invention relates to a photocatalytic composite material and a preparation method thereof, in particular to a titanate nanocone/polyacrylonitrile nanofiber composite material and a preparation method thereof, and belongs to the technical field of photocatalytic materials.
Background
At present, the problem of environmental pollution has become an important problem affecting human survival and development. Solar energy has the advantages of low price, cleanness, reproducibility and the like, and the preparation and application of the semiconductor photocatalytic material can fully develop and utilize the solar energy to help solve the problem of environmental pollution, and is considered to be one of the technologies with the most application prospects for solving the problem of environmental pollution.
The proton titanate has great potential in application in various fields as a functional material, and TiO with the same form as the proton titanate is synthesized simultaneously 2 Also has wide application prospect. Titanate is a novel nano material, has higher photocatalytic effect and special visible region absorption, and has wide application prospect in the aspect of photocatalytic materials. Titanate is a layered semiconductor with better photocatalysis effect discovered at presentMainly due to the large specific surface area and the unique one-dimensional structure, the method is favorable for separating photogenerated electrons from holes.
The preparation method of the one-dimensional titanic acid nano material mainly comprises the following steps: the alkaline thermal method (see: Liu, Y.; Shu, W.; Chen, K.; Peng, Z.; Chen, W.; Acs Catalysis 2012, 2 (12), 2557-,&zhang, z. (2005), Chemistry letters, 34(8), 1168-: watts, J.A. (1970). Journal of Solid State Chemistry, 1(3-4), 319-325.). The strong alkali hydrothermal method is a commonly used method for preparing various one-dimensional titanate nano materials at present. With TiO 2 One-dimensional titanates are prepared from the raw materials under hydrothermal conditions using concentrated alkali, proton titanates are obtained from the resulting alkali metal layered titanates by ion exchange (see: Zhong, l., Liu, y. l., Shu, w., Song, y. b.,&chen, W. (2009). In Advanced Materials Research (Vol.79, pp. 433-436). Trans Tech Publications). The titanate material prepared by strong alkaline hydrothermal process features uniform grain size distribution, less aggregation between grains and higher specific surface area. However, the preparation is carried out under high temperature and high pressure by a concentrated alkali method, the reaction conditions are not mild enough, and the energy consumption is high (see the literature: Liu, Y., Zhong, L., Peng, Z., Cai, Y., Song, Y.,&chen, W. (2011), CrystEngComm, 13(17), 5467-. In addition, the strong alkaline hydrothermal method requires additional treatment of acid solution, which is a relatively large burden on the environment and the production cost.
The powdered photocatalyst has the problems of difficult recovery, easy secondary pollution and the like, and the nanofiber-grade semiconductor material has the advantages of large specific surface area, more reactive sites, simple preparation, small bulk density, difficult agglomeration and the like, so the powdered photocatalyst is emphasized and widely applied in recent years. The nano-fiber membrane loaded with the photocatalyst has potential in degrading pollutants, has a certain self-cleaning effect, and can degrade the pollutants adsorbed on the surface of the composite material. So far, reports of loading one-dimensional titanate on the surface of polyacrylonitrile nano-fiber are not seen.
Disclosure of Invention
Aiming at the defects of the prior art for preparing titanate, the invention provides the composite material for directly synthesizing protonized titanate, which has simple and mild preparation process and is more environment-friendly and loads titanate nanocones on the surface of polyacrylonitrile nanofibers and the preparation method thereof.
The technical scheme for realizing the aim of the invention is to provide a preparation method of titanate nanocone/polyacrylonitrile nanofiber composite material, which comprises the following steps:
(1) according to the mass ratio (0.2-1): dissolving carboxylated polyacrylonitrile powder and polyacrylonitrile powder in a solvent N, N-dimethylformamide or dimethyl sulfoxide to obtain a spinning solution with the mass fraction of 10-20%; preparing a carboxylated polyacrylonitrile nanofiber membrane by adopting an electrostatic spinning process;
(2) the molar ratio (0.1-1): (1-6): (10-50): (200-800), uniformly mixing tetrabutyl titanate, nitric acid, water and ethanol to obtain a mixed solution; soaking the carboxylated polyacrylonitrile nano-fiber membrane prepared in the step (1) in the mixed solution for 6-48 h, and then carrying out forced air drying at the temperature of 20-60 ℃ to obtain amorphous TiO 2 A polyacrylonitrile nanofiber membrane;
(3) the molar ratio of the raw materials is 1: (0.1-2.5): (4-25): (5-20): (500-2000), mixing a titanium source, a morphology control agent, concentrated hydrochloric acid, hydrogen peroxide and deionized water to obtain a mixed solution; the obtained amorphous TiO 2 Soaking the polyacrylonitrile nano-fiber membrane in the mixed solution, placing the polyacrylonitrile nano-fiber membrane on a constant-temperature shaking table for reaction, and then washing and drying by air blast to obtain the titanate nanocone-loaded polyacrylonitrile nano-fiber composite material.
The preparation method of the carboxylated polyacrylonitrile comprises the following steps: the mass ratio of (1-3): mixing itaconic acid or acrylic acid with acrylonitrile, and dissolving the obtained mixture in dimethyl sulfoxide and deionized water in a volume ratio of 1: (1-3) obtaining a solution with the mass fraction of 3% -10%; adding an initiator azobisisobutyronitrile in a nitrogen atmosphere, stirring for pretreatment, and reacting at the temperature of 55-85 ℃; and then carrying out suction filtration, washing and freeze drying to obtain carboxylated polyacrylonitrile powder.
The electrostatic spinning process conditions adopted in the step (1) are that the flow rate is 0.1-0.5 ml/h, the voltage is 6.00-15.00 kv, the receiving distance is 8-15 cm, and the receiver is an aluminum foil or a copper mesh.
Amorphous TiO obtained in the step (2) 2 Soaking the polyacrylonitrile nano-fiber membrane in 0.1-2% hydrochloric acid aqueous solution by mass fraction, treating for 6-12 h at the temperature of 20-80 ℃, washing with water, drying by blast air, and removing incompletely attached amorphous TiO 2 。
The titanium source is one of titanium tetrachloride, tetrabutyl titanate, tetraethyl titanate, isopropyl titanate, titanium trichloride, titanyl sulfate, titanium sulfate and ammonium fluotitanate, or a mixture of more than two of the titanium source and the titanium tetrachloride.
The appearance control agent is one of cyanuric acid, urea, melamine and hexamethyl tetramine, or a mixture of more than two of the cyanuric acid, the urea, the melamine and the hexamethyl tetramine.
And (4) placing the reaction kettle on a constant-temperature shaking table in the step (3) at the reaction temperature of 10-60 ℃ for 12-72 hours.
The technical scheme of the invention also comprises the titanate nanocone/polyacrylonitrile nanofiber composite material prepared by the preparation method.
Compared with the prior art, the invention has the following advantages:
1. the polyacrylonitrile nano-fiber used in the invention is modified to form carboxylated polyacrylonitrile, which provides a certain binding force for loading inorganic particles. Tetrabutyl titanate can form a stable amorphous titanium dioxide sol network on the surface of the nanofiber after being hydrolyzed on the surface of the nanofiber, and the amorphous titanium dioxide sol network is used as a seed layer to facilitate the deposition of titanate, prevent inorganic matters from falling off from the surface of polyacrylonitrile nanofiber and be more beneficial to the recycling of composite materials. The composite material loaded with the titanate nanocones also has a certain self-cleaning effect, and pollutants adsorbed on the surface of the composite material can be degraded.
2. The method has the advantages of avoiding using a high-temperature high-pressure reaction kettle and concentrated alkali, along with low requirements on equipment, greatly reduced energy consumption and wide application prospect.
Drawings
FIG. 1 is an X-ray diffraction diagram of a sample obtained at each step provided by an embodiment of the present invention; wherein, the curve (a) is the X-ray diffraction spectrum of a contrast sample prepared by the carboxylated polyacrylonitrile nano-fiber in the same phase and steps under the condition of not adding a titanium source, and the curve (b) is amorphous TiO 2 The X-ray diffraction spectrum of the polyacrylonitrile nano-fiber composite material, wherein the curve (c) is the X-ray diffraction spectrum of the titanate nanocone/polyacrylonitrile nano-fiber composite material;
FIG. 2 is an SEM scanning electron micrograph of a sample obtained in each step provided by the embodiment of the invention; wherein, the images (a) and (b) are scanning electron microscope images of carboxylated polyacrylonitrile nano-fiber, and the images (c) and (d) are amorphous TiO 2 Scanning electron microscope images of polyacrylonitrile nano-fiber, wherein the images (e) and (f) are scanning electron microscope images of titanate nanocone/polyacrylonitrile nano-fiber;
FIG. 3 is a graph showing the change of absorbance of a sample obtained in the embodiment of the present invention with time under the condition of dark adsorption of a rhodamine B aqueous solution (50 ml in total, with a concentration of 50 mg/L);
FIG. 4 is a graph showing the change of absorbance of a sample in accordance with the embodiment of the present invention with time under the condition that the sample is irradiated with the rhodamine B aqueous solution (total 100ml, concentration is 10 mg/L) by the LED light;
FIG. 5 is a graph showing the change of K/S value with time under LED light irradiation of a dyed fiber membrane obtained after a sample obtained in the example of the present invention is dyed with rhodamine B.
Detailed Description
The technical solution of the present invention is further described with reference to the accompanying drawings and examples.
Example 1
Preparing a carboxylated polyacrylonitrile nanofiber membrane: respectively adding 19.95g of acrylonitrile as a first monomer, 1.05g of itaconic acid as a second monomer, 150ml of dimethyl sulfoxide and 150ml of deionized water into a three-neck flask provided with a mechanical stirring pipe, a condensing pipe and an air guide pipe, starting stirring, introducing nitrogen for 20min, adding 0.21g of azodiisobutyronitrile as an initiator into the system, keeping the nitrogen atmosphere, adjusting the stirring speed to 150rpm, pretreating for 15min, heating to 70 ℃, and reacting for 8 h; and after the reaction is finished, carrying out suction filtration on the reaction liquid, repeatedly washing the obtained powder with deionized water at room temperature, and freeze-drying to obtain acrylonitrile-itaconic acid copolymer powder, wherein the carboxylated polyacrylonitrile is formed by modifying the polyacrylonitrile with itaconic acid. 0.8g of acrylonitrile-itaconic acid copolymer powder and 0.8g of commercially available polyacrylonitrile powder were weighed out and dissolved in 12g N, N-dimethylformamide solution. The carboxylated polyacrylonitrile fiber membrane was dried in a forced air oven by electrospinning with an aluminum foil as a receiver under spinning conditions of a flow rate of 0.2ml/h, a voltage of 7.00kv and a reception distance of 12 cm.
Referring to the drawings (a) and (b) in the attached drawing 2, the drawings are scanning electron microscope images of the carboxylated polyacrylonitrile nanofibers provided in this embodiment, and it can be seen from the images that the nanofibers are uniform, have no beads, and have diameters of 400-700 nm.
And (2) taking the prepared carboxylated polyacrylonitrile fiber membrane with the thickness of 20cm multiplied by 20cm, soaking the carboxylated polyacrylonitrile fiber membrane in a mixed solution containing tetrabutyl titanate (2 g), nitric acid (3 g), water (5.76 g) and ethanol (200 g) for 36h, taking out the carboxylated polyacrylonitrile fiber membrane at intervals of 2h, drying the carboxylated polyacrylonitrile fiber membrane at room temperature, soaking the carboxylated polyacrylonitrile fiber membrane in the mixed solution again, and finally drying the carboxylated polyacrylonitrile fiber membrane at room temperature by air blowing at the temperature of 30 ℃ after water washing.
Soaking the polyacrylonitrile fiber membrane in 100ml of deionized water containing hydrochloric acid (0.5 g), and heating at 80 deg.C for 12 hr to remove incompletely adhered amorphous TiO 2 And after washing with water, air-blast drying.
Will deposit amorphous TiO 2 The polyacrylonitrile nanofiber membrane is soaked in a mixed solution containing titanium tetrachloride (1 ml), cyanuric acid (0.4 g), hydrogen peroxide (5 ml) and concentrated hydrochloric acid (1 ml) and deionized water (120 ml) and reacted for 36 hours at a constant temperature of 35 ℃ on a shaker at a rotating speed of 50 rpm. And taking out the reacted fiber membrane, washing the fiber membrane by using deionized water until the solution is neutral, and performing forced air drying at 40 ℃ to prepare the one-dimensional titanate/polyacrylonitrile nano-fiber composite material.
Referring to FIG. 1, which is an X-ray powder diffraction pattern of the sample provided in this example, the curve (a) is an X-ray diffraction pattern of a comparative sample prepared by a phase synchronization process without adding a Ti source to polyacrylonitrile nanofibers, and (b) is an amorphous TiO 2 X-ray diffraction pattern of polyacrylonitrile nano fiber, and (c) X-ray diffraction pattern of one-dimensional titanate/polyacrylonitrile nano fiber composite material. As can be seen from the figure: 1 sharp crystalline peak at 2 theta =17 degrees and 1 wide amorphous peak at 2 theta =22 degrees are both characteristic peaks of an X-ray diffraction pattern of polyacrylonitrile nano-fiber. The test result of the one-dimensional titanate/polyacrylonitrile nanofiber sample comprises a characteristic peak of polyacrylonitrile and a characteristic peak of titanate.
Referring to FIG. 2, it is an SEM image of the sample provided in this example, wherein (c) and (d) are amorphous TiO 2 Scanning electron microscope images of/polyacrylonitrile nano-fiber, and images (e) and (f) are scanning electron microscope images of one-dimensional titanate/polyacrylonitrile nano-fiber. As shown in fig. 2, the amorphous titanium dioxide is hydrolyzed and then adsorbed on the surface of the polyacrylonitrile nanofiber, and the deposited one-dimensional titanate is uniformly attached to the polyacrylonitrile nanofiber.
Referring to the attached figure 3, it is a graph of the absorbance of the sample obtained in this example with time under the condition of dark adsorption of rhodamine B aqueous solution (total 50ml, concentration 50 mg/L); the concentration of the rhodamine B water solution is greatly reduced by the adsorption of the composite material.
Referring to FIG. 4, the absorbance of the rhodamine B aqueous solution (total 100ml, the concentration is 10 mg/L) of the sample obtained by the embodiment of the invention after the LED light irradiation is shown as a time-varying curve. After the adsorption equilibrium test (illumination for 0 min), the concentration of rhodamine B is reduced, which is benefited from the large specific surface area of the composite material; compared with a pure rhodamine B aqueous solution, the rhodamine B aqueous solution loaded with the one-dimensional titanate/polyacrylonitrile nano-fiber gradually weakens the absorption peak after being irradiated by LED light at different time.
Referring to FIG. 5, the K/S value of a dyed fiber film obtained after a sample obtained by the embodiment of the invention is dyed by rhodamine B under the irradiation of LED light changes along with time.
Example 2
Preparing a polyacrylonitrile nanofiber membrane: 19.95g of acrylonitrile as a first monomer, 1.95g of acrylic acid as a second monomer, 150ml of dimethyl sulfoxide and 150ml of deionized water are respectively added into a three-neck flask provided with a mechanical stirrer, a condenser pipe and an air guide pipe, stirring is started, nitrogen is introduced for 20min, 0.21g of azobisisobutyronitrile as an initiator is added into the system, the nitrogen atmosphere is kept, the stirring speed is adjusted to 150rpm, pretreatment is carried out for 15min, then the temperature is raised to 70 ℃, and the reaction is carried out for 8 h. After the reaction is finished, the reaction solution is filtered, and the obtained powder is repeatedly washed by deionized water at room temperature and freeze-dried to obtain acrylonitrile-acrylic acid copolymer powder. 0.6g of acrylonitrile-acrylic acid copolymer powder and 1.0g of commercially available polyacrylonitrile powder were dissolved in a 10g N, N-dimethylformamide solution. Using a copper mesh as a receiver, electrostatic spinning was carried out under spinning conditions of a flow rate of 0.3ml/h, a voltage of 7.00kv and a reception distance of 14cm, and the resulting fiber film was dried in a forced air oven.
Soaking the polyacrylonitrile fiber membrane 20cm × 20cm in a mixed solution containing tetrabutyl titanate (2 g), nitric acid (3 g), water (5.76 g) and ethanol (200 g) for 48h, taking out every 2h, drying at room temperature, soaking in the mixed solution again, drying the fiber membrane at room temperature, washing with water, and drying by air blowing at 30 ℃.
Soaking the polyacrylonitrile fiber membrane in 100ml of deionized water containing hydrochloric acid (0.25 g), and heating at 60 deg.C for 12 hr to remove incompletely adhered amorphous TiO 2 And after washing, air-blast drying.
Will deposit amorphous TiO 2 The polyacrylonitrile nanofiber membrane of (1) was immersed in a mixed solution containing titanium tetrachloride (0.5 ml), cyanuric acid (0.06 g), hydrogen peroxide (0.56 ml), concentrated hydrochloric acid (0.7 ml) and deionized water (40 ml) and reacted for 72 hours at a rotation speed of 50rpm on a constant temperature shaker at 25 ℃. Taking out the reacted fiber membrane, washing the fiber membrane by deionized water until the liquid is neutral, and drying by blast air to prepare the one-dimensional titanic acidSalt/polyacrylonitrile nanofiber composites.
The sample prepared in this example and the X-ray powder diffraction pattern, the morphology structure, the absorbance change curve of the dye under dark adsorption condition, the absorbance change curve of the dye under photocatalytic condition, and the K/S value change curve of the dyed fiber film obtained after the sample dyeing under LED light irradiation are all similar to those in example 1.
Example 3
Preparing a polyacrylonitrile nanofiber membrane: 19.95g of acrylonitrile as a first monomer, 1.05g of itaconic acid as a second monomer, 150ml of dimethyl sulfoxide and 150ml of deionized water are respectively added into a three-neck flask provided with a mechanical stirrer, a condenser pipe and an air guide pipe, stirring is started, nitrogen is introduced for 20min, 0.21g of azobisisobutyronitrile as an initiator is added into the system, the nitrogen atmosphere is kept, the stirring speed is adjusted to 150rpm, pretreatment is carried out for 15min, then the temperature is raised to 70 ℃, and reaction is carried out for 8 h. And after the reaction is finished, filtering the reaction solution, repeatedly washing the obtained powder with deionized water at room temperature, and freeze-drying to obtain acrylonitrile-itaconic acid copolymer powder. 0.6g of acrylonitrile-itaconic acid copolymer powder and 1.0g of commercially available polyacrylonitrile powder were dissolved in 10g N, N-dimethylformamide solution. Electrospinning was carried out using an aluminum foil as a receiver under spinning conditions of a flow rate of 0.15ml/h, a voltage of 7.00kv and a receiving distance of 12cm, and the resulting fiber film was dried in a forced air oven.
Soaking the polyacrylonitrile fiber membrane 20cm × 20cm in a mixed solution containing tetrabutyl titanate (2 g), nitric acid (3 g), water (5.76 g) and ethanol (200 g) for 36h, taking out every 2h, drying at room temperature, soaking in the mixed solution again, drying the fiber membrane at room temperature, washing with water, and air-drying at 30 ℃.
Soaking the polyacrylonitrile fiber membrane in 100ml of deionized water containing hydrochloric acid (0.5 g), and heating at 60 deg.C for 12 hr to remove incompletely adhered amorphous TiO 2 And after washing, air-blast drying.
Will deposit amorphous TiO 2 Of polyacrylonitrileThe fiber membrane was immersed in a mixed solution containing titanium tetrachloride (0.5 ml), cyanuric acid (1.5 g), hydrogen peroxide (3.5 ml), and concentrated hydrochloric acid (2.5 ml) in deionized water (165 ml) and reacted at a constant temperature of 60 ℃ for 12 hours with a rotation speed of 100rpm on a shaker. And taking out the reacted fiber membrane, washing the fiber membrane by deionized water until the liquid is neutral, and drying by air blast to prepare the one-dimensional titanate/polyacrylonitrile nano-fiber composite material.
The sample prepared in this example and the X-ray powder diffraction pattern, the morphology structure, the absorbance change curve of the dye under dark adsorption condition, the absorbance change curve of the dye under photocatalytic condition, and the K/S value change curve of the dyed fiber film obtained after the sample dyeing under LED light irradiation are all similar to those in example 1.
Claims (5)
1. A preparation method of titanate nanocone/polyacrylonitrile nanofiber composite material is characterized by comprising the following steps:
(1) according to the mass ratio (0.2-1): 1, dissolving carboxylated polyacrylonitrile powder and polyacrylonitrile powder in a solvent N, N-dimethylformamide or dimethyl sulfoxide to obtain a spinning solution with the mass fraction of 10-20%; preparing a carboxylated polyacrylonitrile nanofiber membrane by adopting an electrostatic spinning process;
(2) the molar ratio (0.1-1): (1-6): (10-50): (200-800), uniformly mixing tetrabutyl titanate, nitric acid, water and ethanol to obtain a mixed solution; soaking the carboxylated polyacrylonitrile nanofiber membrane prepared in the step (1) in the mixed solution for 6-48 h, and then carrying out forced air drying at the temperature of 20-60 ℃ to obtain amorphous TiO 2 A polyacrylonitrile nanofiber membrane;
(3) the molar ratio of the raw materials is 1: (0.1-2.5): (4-25): (5-20): (500-2000), mixing a titanium source, a morphology control agent, concentrated hydrochloric acid, hydrogen peroxide and deionized water to obtain a mixed solution; the obtained amorphous TiO 2 Soaking the polyacrylonitrile nanofiber membrane in the mixed solution, placing the mixed solution on a constant-temperature shaking table for reaction, and then washing and drying by air blast to obtain a titanate nanocone/polyacrylonitrile nanofiber composite material;
wherein the morphology control agent is one of cyanuric acid, urea, melamine and hexamethyltetramine, or a mixture of more than two of the cyanuric acid, the urea, the melamine and the hexamethyltetramine;
the reaction temperature of the mixture on a constant temperature shaking table is 10-60 ℃, and the reaction time is 12-72 h.
2. The method for preparing titanate nanocone/polyacrylonitrile nanofiber composite material according to claim 1, wherein: the preparation method of the carboxylated polyacrylonitrile comprises the following steps: the mass ratio of (1-3): mixing itaconic acid or acrylic acid with acrylonitrile, and dissolving the obtained mixture in dimethyl sulfoxide and deionized water in a volume ratio of 1: (1-3) obtaining a solution with the mass fraction of 3% -10%; adding an initiator azobisisobutyronitrile in a nitrogen atmosphere, stirring for pretreatment, and reacting at the temperature of 55-85 ℃; and then carrying out suction filtration, washing and freeze drying to obtain carboxylated polyacrylonitrile powder.
3. The method for preparing titanate nanocone/polyacrylonitrile nanofiber composite material according to claim 1, wherein: the electrostatic spinning process conditions adopted in the step (1) are that the flow rate is 0.1-0.5 ml/h, the voltage is 6.00-15.00 kV, the receiving distance is 8-15 cm, and the receiver is an aluminum foil or a copper mesh.
4. The method for preparing the titanate nanocone/polyacrylonitrile nanofiber composite material according to claim 1, characterized in that: amorphous TiO obtained in the step (2) 2 Soaking the polyacrylonitrile nano-fiber membrane in 0.1-2% hydrochloric acid aqueous solution by mass percent, treating for 6-12 h at the temperature of 20-80 ℃, washing with water, drying by air blowing, and removing incompletely attached amorphous TiO 2 。
5. The method for preparing the titanate nanocone/polyacrylonitrile nanofiber composite material according to claim 1, wherein: the titanium source is one of titanium tetrachloride, tetrabutyl titanate, tetraethyl titanate, isopropyl titanate, titanium trichloride, titanyl sulfate, titanium sulfate and ammonium fluotitanate, or a mixture of more than two of the titanium source and the titanium tetrachloride.
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